Methods for producing and using alkaline aqueous ferric iron solutions

ABSTRACT

Methods for removing reduced sulfur compounds, such as hydrogen sulfide, from fluids employing a ferric iron salt that exhibits unusually high solubility in aqueous, alkaline solutions and has strong affinity for capture and oxidation of reduced sulfur compounds. Alkaline aqueous ferric iron salt and solutions thereof useful for removing reduced sulfur compounds from fluids and various methods of production of such salts and solutions. In addition, methods of regenerating the alkaline aqueous ferric iron salt solutions after capture of hydrogen sulfide or other reduced sulfur compounds, generally by exposure to oxygen in air. The alkali metal carbonate salt preferably comprises potassium carbonate and/or potassium bicarbonate. The alkaline aqueous ferric iron salt solutions generally comprise ferric ions, potassium ions, carbonate ions, and bicarbonate ions, optionally with one or more organic additives. In addition, aqueous-soluble, ferric iron salts and ferric iron containing solids prepared by removal of aqueous medium from solutions herein.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. provisional applications62/924,166, filed Oct. 21, 2019, 63/029,405, filed May 23, 2020, and63/032,600, filed May 30, 2020, each of which is incorporated byreference herein in its entirety.

BACKGROUND

Hydrogen sulfide (H₂S) is an extremely corrosive and poisonous gascommonly present in natural gas, oil, biogas and geothermal steams.Hydrogen sulfide removal is necessary for energy production and variousindustrial processes, such as the production of natural gas, oil, paper,geothermal energy and biological gas (e.g., from landfills, dairies, andwastewater treatment plants). Various technologies exist for hydrogensulfide removal, such as chemical scavengers (e.g., ferric chloride,monoethanolamine triazine), the Amine-Claus process, liquid redoxprocesses, and packed bed technologies (e.g., SulfaTreat® (M-I LLC,Houston Tex.) and Iron Sponge technologies). Hydrogen sulfide scavengersare a very common method of hydrogen sulfide control. Hydrogen sulfidescavengers are commonly iron-based compounds that react with H₂S andconvert it to iron sulfide or pyrite. While effective, these single usechemical technologies consume natural resources, produce hazardouschemical waste, and have high operating costs. There remains asignificant need in the art for methods and materials for hydrogensulfide control appropriate for a variety of industrial application andwhich are cost-effective.

SUMMARY OF THE INVENTION

The present invention relates to methods and materials for removal ofhydrogen sulfide and other reduced sulfur compounds from fluids,including gases and liquids, containing such reduced sulfur compounds.The method involves contacting the fluid with an alkaline aqueoussolution containing a selected concentration of ferric ion, Fe(III),wherein the ferric ion is at least substantially or completely dissolvedin the aqueous medium forming a solution. Contacting results in captureand oxidation of at least a portion of the reduced sulfur compounds inthe fluid, the concomitant formation of ferrous ion, Fe(II), and theformation of Fe(II) sulfide particles which are suspended in the aqueoussolution and at least partial removal of reduced sulfur compounds fromthe fluid. After contact with the fluid, the at least partially reducedalkaline aqueous solution used to remove reduced sulfur and the ferroussulfide particles suspended in it can be regenerated by treatment withoxygen in air or an alternative oxidizing agent resulting in formationof elemental sulfur which precipitates from the solution and can becollected. In embodiments, capture of the reduced sulfur compoundresults in formation of one or more iron sulfides, such as, FeS, atleast in part as a solid which can be separated from the at leastpartially reduced aqueous solution, if desired. Iron sulfides can beconverted via oxidation to elemental sulfur and ferric iron as is knownin the art.

In general, ferric iron salts are virtually insoluble in aqueoussolutions above pH 6. In one aspect, the present invention relates tomethods for producing ferric iron salts that are unusually soluble inaqueous solutions under alkaline conditions. In one embodiment of theinvention, these salts contain anionic ferric-bicarbonate complexes,anionic ferric-carbonate complexes or anionicferric-carbonate/bicarbonate complexes, optionally with hydroxyl groups,that are negatively charged and that, unlike free ferric cations, arefully water soluble under alkaline conditions. In embodiments,water-soluble ferric iron salts comprise carbonate, bicarbonate or amixture thereof. In embodiments, water-soluble ferric iron complexescomprise carbonate, bicarbonate or a mixture thereof and hydroxide. Inembodiments, the counter-ion of the anionic water-soluble ferric ironcomplexes is potassium. In embodiments, water-soluble ferric iron saltsmay be a mixture of different salts.

The present invention also relates to aqueous-soluble, ferric ironsalts, aqueous solutions containing such salts and to solids prepared byremoving water and aqueous solvent from such solutions. The inventionalso relates to water-soluble ferric salts that can be purified orisolated from the alkaline aqueous ferric iron salt solution, forexample, by extraction of alkaline aqueous ferric iron salt solutions,as described in examples herein, or precipitation by addition of one ormore organic solvents to the alkaline aqueous ferric iron saltsolutions. The ferric iron salts and ferric iron-containing solids ofthis invention and aqueous solutions in which such salts and solids aredissolved are useful in various industrial processes. Water and aqueoussolutions comprising these salts are particularly useful for removal ofreduced sulfur compounds (e.g., H₂S) from fluids. Certain solutions ofthis invention are also useful for at least partial removal of CO₂ fromfluids containing CO₂. Certain solutions of this invention are alsouseful for the removal of oxygen from fluids. Simultaneous removal ofhydrogen sulfide, carbon dioxide and oxygen may be very useful intreating biogas streams, which often contain these gases.

Various methods of synthesis of the water- or aqueous-soluble, ferriciron salts are provided herein.

Furthermore, the present invention relates to methods for using thealkaline aqueous ferric iron salt solutions to treat reducedsulfur-containing fluids. For instance, the alkaline aqueous ferric ironsalt solutions may be used to treat H₂S-containing gases (e.g., naturalgas, biogas, acid gas, geothermal vent gas or foul air from farming,industrial or wastewater operations).

Ferric iron (Fe³⁺) is soluble in acidic aqueous solutions (e.g., belowpH 5). Above about pH 5, ferric iron is typically insoluble in water andwill form particles of one or more of the known iron oxides (e.g.,ferric oxide, ferric oxyhydroxides). The methods of the presentinvention enable the production of alkaline aqueous solutions havingsolubilized ferric iron salts that are extremely effective for thetreatment of reduced sulfur-containing fluids. In contrast toconventional methods of solubilizing ferric iron at high pH, suchalkaline aqueous ferric iron salt solutions may be produced with orwithout organic additives as described in greater detail below.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an embodiment of a method for treating a reducedsulfur-containing fluid with an alkaline aqueous ferric iron solution.

FIG. 2 is a schematic drawing of an exemplary system for treating areduced-sulfur containing fluid with an alkaline ferric iron saltsolution of this invention and regenerating the alkaline ferric ironsalt solution after use.

FIG. 3 is a UV-Vis spectrum of purified alkaline ferric iron saltsolution diluted in buffer as described in Example 6.

FIG. 4 is a graph illustrating pH change with carbon dioxide capture andrelease by aqueous alkaline ferric iron salt solutions as described inExample 8.

DETAILED DESCRIPTION

The invention relates to methods and materials for removing reducedsulfur compounds, particularly hydrogen sulfide (H₂S), from fluidscontaining such reduced sulfur compounds. Materials include alkalineferric iron salt solutions that can be used to scrub reduced sulfurcompounds from the fluids. In embodiments, materials include ferric ironsalt solutions that self-assemble into complexes that are unusuallysoluble in alkaline solutions, and that can be efficiently used to scrubreduced sulfur compounds from the fluids. Materials also include ferriciron-containing solid materials or salts that can be used to preparealkaline ferric iron solutions useful in methods herein. The inventionfurther provides methods for making alkaline ferric iron salts solutionsherein as well as methods for making water-soluble ferric iron salts andferric iron containing materials which are useful at least forpreparation of alkaline ferric iron salt solutions herein.

In embodiments, the invention provides a method for removing reducedsulfur compounds from fluids. In embodiments, the fluids are gases. Inembodiments, the fluids are liquids. In particular embodiments thereduced sulfur compound is hydrogen sulfide. The methods herein areparticularly useful for treatment of gases, such as hydrocarboncontaining gases containing hydrogen sulfide. Fluids containing hydrogensulfide may, in embodiments, also contain one or more other reducedsulfur compound, such as mercaptans, alkyl disulfides, carbonyl sulfideor carbon disulfide. Fluids containing hydrogen sulfide and/or otherreduced sulfur compounds, may, in embodiments, also contain carbondioxide, oxygen or a combination thereof.

In embodiments, the method for removing reduced sulfur compoundsinvolves contacting an alkaline aqueous ferric iron salt solution asdescribed herein with a reduced sulfur-containing fluid, which containsat least one reduced sulfur compound. In embodiments, the alkalineaqueous ferric iron salt solution comprises ferric ions (Fe³⁺),potassium ions (K⁺), carbonate ions (CO₃ ²⁻) and bicarbonate ions (HCO₃⁻), optionally hydroxide and nitrate ions and optionally contains one ormore organic additives. Contacting the ferric iron salt solution and thereduced sulfur-containing fluid produces a reduced alkaline ferric ironsolution, and comprises oxidizing at least a portion of the at least onereduced sulfur compound in the fluid and reducing at least a portion ofthe ferric ions in the solution to ferrous ions (Fe²⁺). Contacting alsoresults in forming one or more iron sulfide compounds in the alkalineaqueous ferric iron solution and thereby removes at least a portion ofthe reduced sulfur compounds from the fluid. It is believed that thedirect reaction of iron with sulfide to form iron sulfide distinguishesthis chemistry from other “liquid redox” processes that use organicchelating agents to solubilize iron. In embodiments, at least someportion of the ferric iron remains dissolved in the alkaline ferric ironsolution during contacting.

In embodiments, the method further comprises removing iron sulfidecompounds from the alkaline at least partially reduced aqueous ferriciron solution after removal of at least a portion of the reduced sulfurcompounds from the fluid. In embodiments, the method further comprisesseparation of iron sulfide compounds from the alkaline at leastpartially reduced aqueous ferric iron solution by precipitation,settling, centrifugation or filtration. Such separation can beaccomplished by methods that are well known in the art. In embodiments,the method further comprises oxidizing at least a portion of the ferrousiron formed in the reduced alkaline aqueous ferric iron solution back toferric iron to at least in part regenerate the aqueous ferric ironsolution. In embodiments, the method further comprises exposing thereduced alkaline iron solution to an oxidizing agent to oxidize at leasta portion of the ferrous ions to ferric ions, thereby producing at leasta partially regenerated alkaline aqueous ferric iron salt solution. Inembodiments, the exposing step comprises producing elemental sulfur.

In embodiments, prior to the contacting step, the alkaline aqueousferric iron salt solution comprises at least some iron-based particles,and wherein due to at least one of the contacting step (a), theproducing step (b) and the exposing (oxidizing) step (c), theregenerated alkaline aqueous ferric iron solution is free of iron-basedparticles.

In embodiments, the process for removal of reduced sulfur compounds is acontinuous process. In embodiments, the contacting step (a), theproducing step (b), and the exposing step (c) occur concomitantly, ifpresent. In embodiments, the method comprises repeating steps (a)-(c) atleast once.

In embodiments of the method, a flow of fluid is contacted with thealkaline aqueous ferric solution for a selected contact time to removereduced sulfur compounds from the fluid to provide a purified fluid. Inembodiments, after contact with fluid, the alkaline at least partiallyreduced ferric iron solution contains at least one iron sulfide andthereafter the iron sulfide is oxidized to elemental sulfur and ferricions in the at least partially reduced alkaline aqueous ferric solution.In embodiments, such removal is continuous. In embodiments, the at leastpartially reduced alkaline aqueous ferric solution is oxidized to atleast in part regenerate the alkaline aqueous ferric solution. Oxidationcan be performed by contacting the at least in part reduced ferric ironsalt solution with oxidizing agents, such as oxygen in air or anotheroxygen-containing gas.

In embodiments, the alkaline aqueous ferric iron salt solution comprisesferric ions (Fe³⁺); potassium ions (K⁺); wherein the molar ratio of thepotassium ions to the ferric ions is at least 1.0; carbonate ions (CO₃²⁻); bicarbonate ions (HCO₃ ⁻); and optionally nitrate ions. Inembodiments the alkaline aqueous iron salt solution comprisesferric-carbonate complexes that are anionic in nature and exhibitunusually high solubility in alkaline solutions. In embodiments, thealkaline aqueous ferric iron salt solution comprises nitrate ions. Inembodiments, the alkaline aqueous ferric iron salt solution comprisesbicarbonate ions.

In embodiments, the alkaline aqueous ferric iron salt solution containslevels of halide ion of not greater than 10,000 ppm. In embodiments, thealkaline aqueous ferric iron salt solution contains levels of halide ionof not greater than 1,000 ppm. In embodiments, the alkaline aqueousferric iron salt solution contains levels of halide ion of not greaterthan 100 ppm. In embodiments, the alkaline aqueous ferric iron saltsolution contains levels of halide ion of not greater than 10 ppm. Inembodiments, the alkaline aqueous ferric iron salt solution does notcontain detectible levels of halide ions. In embodiments, the alkalineaqueous ferric iron salt solution contains levels of chloride ion of notgreater than 10,000 ppm. In embodiments, the alkaline aqueous ferriciron salt solution contains levels of chloride ion of not greater than1,000 ppm. In embodiments, the alkaline aqueous ferric iron saltsolution contains levels of chloride ion of not greater than 100 ppm. Inembodiments, the alkaline aqueous ferric iron salt solution containslevels of chloride ion of not greater than 10 ppm. In embodiments, thealkaline aqueous ferric iron salt solution does not contain detectiblelevels of chloride ions.

In embodiments, the alkaline aqueous ferric iron salt solution containslevels of sulfate ion of not greater than 10,000 ppm. In embodiments,the alkaline aqueous ferric iron salt solution contains levels ofsulfate ion of not greater than 1,000 ppm. In embodiments, the alkalineaqueous ferric iron salt solution contains levels of sulfate ion of notgreater than 100 ppm. In embodiments, the alkaline aqueous ferric ironsalt solution contains levels of sulfate ion of not greater than 10 ppm.In embodiments, the alkaline aqueous ferric iron salt solution does notcontain detectible levels of sulfate ions. In embodiments, the alkalineaqueous ferric iron salt solution contains levels of sodium ion of notgreater than 10,000 ppm. In embodiments, the alkaline aqueous ferriciron salt solution contains levels of sodium ion of not greater than1,000 ppm. In embodiments, the alkaline aqueous ferric iron saltsolution contains levels of sodium ion of not greater than 100 ppm. Inembodiments, the alkaline aqueous ferric iron salt solution containslevels of sodium ion of not greater than 10 ppm. In embodiments, thealkaline aqueous ferric iron salt solution does not contain detectiblelevels of sodium ions. In embodiments, the alkaline aqueous ferric ironsalt solution does not contain NaCl. In embodiments, the alkalineaqueous ferric iron salt solution does not contain ethanol. Inembodiments, the alkaline aqueous ferric iron salt solution does notcontain an alcohol having 1-6 carbon atoms.

In embodiments, the alkaline aqueous ferric iron salt solution comprisesone or more organic additives, other than organic solvents. Inembodiments, the one or more organic additives are chelating agents. Inembodiments, any organic additives, other than organic solvents, arepresent in the solution at concentrations such that the molar ratio offerric ion in the solution to each organic additive is at least 2. Inembodiments, wherein the solutions comprise one or more organicadditives, ferric ions are present in the solution in molar excess, forinstance at least 3-, at least 5-, at least 10- or at least 20-foldmolar excess, over each of the organic additives. In embodiments, thealkaline aqueous ferric iron salt solution does not contain a chelatingagent. In embodiments, the alkaline aqueous ferric iron salt solutiondoes not contain EDTA ions.

In embodiments, the alkaline aqueous ferric iron salt solution is madeby dilution of a concentrate. In embodiments, the concentrate is dilutedfrom 1- to up to 60-fold with an aqueous medium, and in particularembodiments, the aqueous medium used for dilution is a potassiumcarbonate/bicarbonate buffer. In a more specific embodiment, theconcentrate is diluted from 10-to 30-fold with an aqueous medium, andparticularly with a potassium carbonate/bicarbonate aqueous buffer. Anunusual aspect of the alkaline aqueous ferric iron salt is that theconcentrate is preferably diluted into potassium carbonate/bicarbonatebuffer, rather than water. Dilution into water often results inprecipitation of iron oxide particles, whereas dilution into potassiumcarbonate/bicarbonate buffer results in fully soluble alkaline aqueousferric iron salt solutions. Aqueous media used to dilute ferric ion saltsolutions for use in methods herein can include other ionic or non-ioniccomponents that do not deleteriously affect and may enhance solubilityof the ferric ions therein.

a. Methods of Synthesis

Broadly, the present patent application also relates to methods forproducing and using alkaline aqueous ferric iron salt solutions. Asdescribed in greater detail below, the new alkaline aqueous ferric ironsalt solutions may be produced and regenerated onsite via a variety ofmethods at substantially lower cost and chemical consumption thancompeting H₂S control technologies.

i. Aqueous Synthesis Methods

Aqueous synthesis methods of producing the new alkaline aqueous ferriciron salt solutions generally include reacting at least one ferric ironsalt reagent with at least one alkali metal carbonate salt reagent. Insome embodiments, the at least one ferric iron salt reagent comprisesferric nitrate (Fe(NO₃)₃). Generally, the at least one alkali metalcarbonate salt reagent comprises potassium carbonate, or potassiumbicarbonate and combinations thereof. The ferric iron salt reagent maybe in any suitable form, such as dissolved in aqueous solution or as adry or hygroscopic solid. For instance, in embodiments where at leastsome ferric nitrate is used as a solid, the ferric nitrate may be in theform of the hexahydrate salt, or the nonahydrate salt and combinationsthereof. An acidic aqueous solution comprising a ferric salt may beproduced, for instance, by solubilizing the ferric iron from scrap metal(e.g., iron or steels) using an acidic solution (e.g., nitric acid toproduce a ferric nitrate solution).

Similarly, the potassium carbonate and potassium bicarbonate may be inany suitable form. For instance, potassium carbonate may be used in theform of the anhydrous salt, or the sesquihydrate salt (K₂CO₃.1.5H₂O) andcombinations thereof. As discussed in greater detail below, while notbeing bound by any theory, it is believed that at least the carbonateions complex with and greatly enhance the solubility of the ferric ironin the alkaline aqueous ferric iron solutions. Furthermore, alkalineferric iron salt solutions comprising nitrate may be preferred sincesimilar mixtures made from different ferric and alkali metal salts maynot form alkaline aqueous ferric iron solutions that are free ofprecipitates (e.g., particles such as ferric iron-based particles) (seeExample 1). In embodiments, water-soluble ferric salts can be employedas the ferric iron salt reagent. In specific embodiments, the ferriciron salt reagent is not ferric chloride. In specific embodiments, theferric iron salt reagent is not ferric sulfate.

As used herein, “alkali metal carbonate salt” means a carbonate salt ofone or more of the alkali metals (e.g., Li, Na and K). Thus, for thepurposes of this patent application, carbonate salts of the alkalineearth metals (e.g., Ba, Mg, Ca, Sr) do not fall within the scope of theterm, “alkali metal carbonate salt.”

The term “alkaline aqueous solution” refers to an aqueous solution of pHgreater than 7.0. Preferred alkaline aqueous solutions are those havingpH greater than 8.0. Alkaline solutions include those having pH between9-13. The terms aqueous solution and aqueous medium also includemiscible mixtures of water with organic solvents, wherein water is thepredominant component (at least 50% by volume) of the aqueous medium orsolution. In specific embodiments, one or more organic solvents whichare water soluble, such as ethanol, are present in the aqueous medium upto 20% by volume. In specific embodiments, one or more water-solubleorganic solvents, such as ethanol are present in the aqueous medium upto 10% by volume.

After the reacting step described above, the resulting alkaline aqueousferric iron salt solutions generally comprise ferric ions (Fe³⁺),potassium ions (K⁺), carbonate ions (CO₃ ²⁻) and bicarbonate ions (HCO₃⁻), optionally with one or more organic additives. As discussed ingreater detail below, the molar ratio of the potassium ions to theferric ions is generally at least 2.0

While not being bound by any theory, it is believed that the ability ofthe ferric iron to remain highly soluble in alkaline solutions is due tothe composition of the novel ferric iron salt, specifically theformation of ferric ion complexes with carbonate, bicarbonate and/orhydroxide or nitrate ions that are anionic in nature. It is furtherbelieved that the ability of the ferric iron to remain highly soluble inalkaline solutions is due to the self-assembly of ferric ions withcarbonate, bicarbonate and/or hydroxide or nitrate ions to formcomplexes that are anionic in nature. As such, any suitable aqueoussynthesis pathway (e.g., the specific reagents used or the order ofcombining reagents) may be chosen to produce the alkaline aqueous ferriciron salt solutions. Some suitable methods are described below.

As used herein, an “aqueous solution” includes (1) a solution where thepredominating solvent (greater than 50% by volume) is water and (2)water. In the case that water is used, the water may be a purified formof water, such as deionized water or distilled water. As noted above,aqueous medium can be a miscible mixture of water and a water-solubleorganic solvent. Such aqueous media are single phase, showing no visiblephase separation. The term solution is used herein to distinguish oversuspensions comprising particles and more particularly to distinguishsolutions comprising ferric ions complexes in aqueous medium fromsuspensions containing iron-based precipitates. For instance,suspensions of iron oxides such as ferrihydrite, hematite, akaganéite,goethite, lepidocrocite, and magnetite are distinguished from solutionscomprising soluble iron ions or soluble, anionic iron-carbonatecomplexes. In embodiments herein, solutions, even when colored, aregenerally transparent on visual inspection. In embodiments herein,solutions have no suspended particles on visual inspection. Inembodiments herein, solutions after being subjected to centrifugation donot have a solid pellet by visual inspection. In embodiments herein,solutions that are filtered through 0.3 micron filter paper show novisible solid particles on the filter. In embodiments herein, thesolution may be a colloid solution as that term is understood in theart. In embodiments herein, the solution is not a colloid solution asthat term is understood in the art. In embodiments herein, the solutiondoes not exhibit a Tyndall effect as that effect is understood in theart.

The term solution is used herein as broadly as it is used in the art. Inan embodiment, the term solution refers to a solution of a solid,particularly a salt, in water or an aqueous medium. Herein, a solid issoluble in water or an aqueous medium, if 1 or more grams of the soliddissolve in 100 mL of water or the aqueous medium, which may be analkaline buffer. In embodiments, preferred solids and salts of thisinvention are very soluble in water or an aqueous medium such that 2 ormore grams of the solid or salt dissolve in 100 mL of water or aqueousmedium, such as alkaline buffer. Solubility is assessed at ambient roomtemperature (25° C.) and ambient pressure (1 atmosphere). It will beappreciated that solubility of a given solid in a given solvent can beaffected by the presence of other solutes in the water or aqueousmedium. In embodiments, certain salts and solids of this invention aresoluble in water or aqueous medium such that 0.1 gram or more of salt orsolid dissolves in 100 mL of the water or aqueous medium. Inembodiments, certain salts and solids of this invention are soluble inwater or aqueous medium such that 0.5 gram or more of salt or soliddissolves in 100 mL of the water or aqueous medium. In embodiments,certain salts and solids of this invention are soluble in water oraqueous medium such that 1 gram or more of salt or solid dissolves in100 mL of the water or aqueous medium. In embodiments, certain salts andsolids of this invention are soluble in water or aqueous medium at alevel of 5 or more grams/100 mL water or medium. In embodiments, certainsalts and solids of this invention are soluble in water or aqueousmedium at a level of 50 or more grams/100 mL water or medium.

In one embodiment, reacting the reagents comprises combining a firstaqueous solution and a second aqueous solution. In one embodiment, thefirst aqueous solution comprises the at least one ferric iron saltreagent and the second aqueous solution comprises the at least onealkali metal carbonate salt reagent. The first aqueous solution and/orthe second aqueous solution may comprise at least one of the one or moreorganic additives. Furthermore, at least one of the one or more organicadditives may be added to the produced alkaline aqueous ferric ironsolution.

As noted above, the required reagents are at least one ferric iron saltand at least one alkali metal carbonate salt. Due in part to the acidicnature of the at least one ferric salt and the basic nature of thealkali metal carbonate salt, the contacting step results in a vigorous,somewhat exothermic reaction that generates carbon dioxide gas. At leastsome of the generated carbon dioxide is released from the reactionmixture as a gas. In an embodiment, 10% or more of the total CO₂ incarbonate is released. In embodiments, up to 20% of the total carbonatein CO₂ is released.

As used herein, “organic additives” means any molecule having at leastone carbon atom and at least one hydrogen atom. Organic additivesinclude among others include one or more chelating agent. Organicadditive reagents may be included in any suitable form. For instance,ethylenediaminetetraacetic acid (“EDTA”) may be included in its acidicform (EDTA) or any of its salt forms (e.g., Na₂EDTA, Na₄EDTA, K₂EDTA andK₄EDTA).

In some embodiments, the reacting comprises fully combining the at leastone ferric iron salt reagent with the alkali metal carbonate saltreagent to produce the alkaline aqueous ferric iron solution. In anembodiment, ferric iron reagent is converted on reaction to awater-soluble alkaline ferric iron salt. The resulting alkaline aqueousferric iron salt solutions are preferably free of particles, such asiron-based particles. In embodiments, a step of filtering, settling, orcentrifugation can be employed to remove precipitate formed on reaction,so long as the filtered or centrifuged solution is stable to furtherprecipitation of solid or salt from the solution. In embodiments, nostep of filtering, settling, or centrifugation is required because afully soluble solution is formed.

The presence of particles, particularly iron-oxide- oroxyhydroxide-based particles, in the alkaline aqueous ferric ironsolution is not preferred for several reasons. For instance, contactingthe alkaline aqueous ferric iron solutions with a reducedsulfur-containing fluid and exposing the resulting solution to anoxidizing agent produces elemental sulfur. Elemental sulfur is insolublein water and in the alkaline aqueous ferric iron solutions of thepresent invention. Accordingly, the elemental sulfur is generallyremoved by a simple liquid-solid separation process that results in highrecovery of the alkaline aqueous ferric iron solution, thus minimizingloss of the active ferric iron. Conversely, iron-based particles tend toembed themselves in elemental sulfur, thereby resulting in the loss offerric iron in such liquid-solid separation processes. Thus, thepresence of iron-based particles in alkaline aqueous ferric ironsolutions is not preferred. Furthermore, while not being bound by anytheory, it is believed that the presence of particles (e.g., iron-basedparticles) may promote (e.g., catalyze) the formation of other,chemically unreactive or less reactive iron-based particles from thealkaline aqueous ferric iron solutions, resulting in the loss of activeiron as a reduced sulfur capture agent.

As noted above, the alkaline aqueous ferric iron salt solutions arepreferably free of particles (e.g., free of iron-based particles).However, the inventors of the present invention have found thatparticles may sometimes form after production of more highlyconcentrated alkaline aqueous iron solutions. For instance, an alkalineaqueous ferric iron solution that is supersaturated with ferric iron maybe thermodynamically unstable and precipitate iron-based particles. Insome instances, these alkaline aqueous iron solutions are free of anyorganic additives. However, such iron-based particles may be dissolvedinto solution with the addition of organic additives at lowconcentrations (e.g., sub-stoichiometric) as described herein.Alternatively, such particles may be filtered from the solution.Unexpectedly, the inventors of the present invention have found that analkaline aqueous ferric iron solution comprising at least some particles(e.g., iron-based particles) may be contacted with a reducedsulfur-containing fluid and subsequently exposed to an oxidizing agent,e.g., air or oxygen, thereby producing an alkaline aqueous ferric ironsolution that is free of particles.

As used herein, “free of particles” means that an alkaline aqueousferric iron solution is visually free of any particles. In oneembodiment, an alkaline aqueous ferric iron solution is free ofiron-based particles. As used herein, “iron-based particles” means anyparticles (e.g., precipitates) comprising iron that may form during orafter production of alkaline aqueous ferric iron salt solutions. Forinstance, iron-based particles may be iron oxides, iron oxyhydroxides,mixed metal oxides and any combinations thereof. In one embodiment, analkaline aqueous ferric iron solution is free of iron oxide particles(e.g., ferrihydrite, hematite, akaganeite, goethite, lepidocrocite, andmagnetite).

Iron-based particles can be detected in general by any analytical methodknown in the art. For example, iron-based particles can be detected byfiltration of any precipitate from liquid medium followed by analyzingthe precipitate using inductively coupled plasma (ICP).

ii. Additional Methods

As noted above, alkaline aqueous ferric iron salt solutions may beproduced and subsequently employed for the treatment of fluidscomprising reduced sulfur compounds (e.g., H₂S). In addition to suchsyntheses, alkaline ferric iron salt solutions can be produced fromintermediate forms, including at least partially reacted solid mixturesand at least partially reacted wet solid mixtures. For instance, such atleast partially reacted mixtures may be produced by combining solids ofa ferric iron salt reagent and an alkaline carbonate salt reagent,optionally with one or more first organic additives, followed byforceful mixing (e.g., ball milling) to react at least some of thereagents. The term ferric iron salt reagent is used to designate theferric iron salt that is used to prepare the solutions of the inventionand to distinguish that salt reagent from the soluble ferric iron saltthat is formed during preparation. This mixing may be done in theabsence of added water (note that water can be present in salts andsolids, such as is present in the ferric nitrate hexahydrate salt and/orferric nitrate nonohydrate salt) or with an amount of water or aqueousmedium that is insufficient to fully solubilize and react the ferriciron salt and/or alkali metal carbonate reagents. The solution is thenprepared by adding water or aqueous medium to fully solubilize theferric iron salt formed on reaction.

iii. Drying and Rehydration

After their production, the alkaline aqueous ferric iron salt solutions,those that are concentrated, may be diluted for use in treating reducedsulfur-containing fluids. It has been found that diluting alkalineaqueous ferric iron salt can be done by adding a concentrated alkalineaqueous ferric iron solution to an aqueous alkali metal carbonatesolution or an aqueous alkali metal carbonate-bicarbonate buffer. In anembodiment, for example, the concentrated alkaline aqueous ferric ironsolution is added to an aqueous alkali metal carbonate-bicarbonatebuffer (e.g., an aqueous potassium carbonate-bicarbonate buffer) of pHrange 8.5-11. Diluting alkaline aqueous ferric iron salt solutions in anaqueous metal carbonate or aqueous metal carbonate-bicarbonate buffermay be preferred as it has been found that substantially dilutingalkaline aqueous ferric iron solutions with aqueous solutions atcircum-neutral pH (e.g., distilled water, deionized water) may lead tothe formation of iron-based particles.

After their production, alkaline aqueous ferric iron salt solutions maybe dried to form a solid ferric iron-containing salt mixture that may berehydrated to form alkaline aqueous ferric iron salt solutions. Forinstance, the drying may be performed by evaporation or spray drying andcombinations thereof, among other methods. After drying, the solidmaterials may be rehydrated, for instance, using an aqueous solution(e.g., water), an aqueous alkali metal carbonate solution and/or anaqueous alkali metal carbonate-bicarbonate buffer solution (e.g., anaqueous potassium carbonate-bicarbonate buffer solution). Therehydration solution may be added to the solid material or vice-versa.Such solid ferric iron-containing mixtures may advantageously beproduced at a centralized processing facility, then subsequently dilutedat a location closer to the point of usage.

b. Products and Composition

i. Alkaline Aqueous Ferric Iron Solutions

Generally, the resulting alkaline aqueous ferric iron salt solutions ofthe present invention comprise ferric ions (Fe³⁺), potassium ions (K⁺),carbonate ions (CO₃ ²⁻) and bicarbonate ions (HCO₃ ⁻). In someembodiments, an alkaline aqueous ferric iron salt solution furthercomprises at least some hydroxide ion (OH⁻) or nitrate ion (NO₃ ⁻). Insome embodiments, an alkaline aqueous ferric iron solution comprises oneor more organic additives. In some preferred embodiments, an alkalineaqueous ferric iron salt solution is free of particles. In someembodiments, an alkaline aqueous ferric iron solution is free of ferriciron-based particles.

In embodiments, the alkaline aqueous ferric iron salt solutions have aconcentration of ferric iron from 0.005 to 5.0 mols/L. Higherconcentration alkaline aqueous ferric iron salt solutions may beproduced with precipitated solids (e.g., water-soluble iron-basedsolids) therein that may dissolve upon the addition of an aqueoussolution (e.g., water or an alkaline aqueous buffered solution). The pHof the alkaline aqueous ferric iron solutions may generally be from 8.0to 13.0. In one embodiment, the pH of an alkaline aqueous ferric ironsalt solution is at least 8.0. In another embodiment, the pH of analkaline aqueous ferric iron salt solution is at least 8.5. In yetanother embodiment, the pH of an alkaline aqueous ferric iron saltsolution is at least 9.0. In another embodiment, the pH of an alkalineaqueous ferric iron salt solution is at least 9.5. In anotherembodiment, the pH of an alkaline aqueous ferric iron salt solution isat least 10.0. In yet another embodiment, the pH of an alkaline aqueousferric iron salt solution is at least 10.5. In another embodiment, thepH of an alkaline aqueous ferric iron salt solution is at least 11.0. Inyet another embodiment, the pH of an alkaline aqueous ferric iron saltsolution is at least 11.5. In one embodiment, the pH of an alkalineaqueous ferric iron salt solution is not greater than 13.0. In anotherembodiment, the pH of an alkaline aqueous ferric iron salt solution isnot greater than 12.5. In yet another embodiment, the pH of an alkalineaqueous ferric iron salt solution is not greater than 12.0. In anotherembodiment, the pH of an alkaline aqueous ferric iron salt solution isnot greater than 11.5. In yet another embodiment, the pH of an alkalineaqueous ferric iron salt solution is not greater than 11.0.

In embodiments, the alkaline aqueous ferric iron salt solution has a pHof at least 8, or at least 8.5, or at least 9, or at least 9.5, or atleast 10, or at least 10.5, or at least 11.0; or between 8 and 13.5; orbetween 8.5 and 13.5; or between 9 and 13.5 or between 10 and 13.5; orbetween 10.5 and 13.5; or between 11 and 13.5 or between 9 and 12.5; orbetween 9.5 and 12; or between 9 and 11; or between 9 and 10; or between11 and 13.5; or between 11 and 13; or between 11 and 12; or between 12and 13.5; or between 12 and 13; or 9, or 10 or 11 or 12 or 13.

ii. Solid Products

As noted above, the alkaline aqueous ferric iron solutions may beproduced from an intermediate solid material and/or the solid materialproduced by drying an alkaline aqueous ferric iron salt solution (i.e.,a “solid ferric iron-containing material”). Such solid products may havethe advantage of decreased storage space and lower shipping costs to thepoint of use, among others. While not being bound by any theory, it isbelieved that the ferric iron salt in these materials may be present asa complex ferric metal salt, where the mixed metal salt comprises theferric iron ions and one or more of potassium ions, carbonate ions,bicarbonate ions, nitrate ions (when present), hydroxide ions, andwater. In embodiments, the mixed metal potassium/ferric salt formed onreacting as described herein is soluble in water or aqueous medium. Inspecific embodiments, the molar ratio of potassium ions to ferric ionsin the salt is 3 or more. In embodiments, the salt can be a mixture ofone or more of such mixed metal salts. In an embodiment, the saltcomprises K₆[Fe₂(OH)₂(CO₃)₅]. In specific embodiments, the molar ratioof potassium ions to ferric ions in the alkaline aqueous salt solutionis 6 or more, or 6.6 or more, or 7 or more, or 8 or more, or 9 or more,or 10 or more, or 11 or more, or 12 or more.

In embodiments, salts and solids of the invention do not contain nitrateions at levels greater than 10,000 ppm, or at levels greater than 1,000ppm, or at levels greater than 100 ppm or at levels greater than 10 ppmor at detectible levels. In embodiments, salts and solid of theinvention do not contain chloride ions (Cl⁻) at levels greater than10,000 ppm, or at levels greater than 1,000 ppm, or at levels greaterthan 100 ppm or at levels greater than 10 ppm or at detectible levels.In embodiments, salts and solid of the invention do not contain halideions (e.g., Cl⁻, Fl⁻, Br⁻) at levels greater than 10,000 ppm, or atlevels greater than 1,000 ppm, or at levels greater than 100 ppm or atlevels greater than 10 ppm or at detectible levels. In embodiments,salts and solid of the invention do not contain sodium chloride (NaCl)at levels greater than 10,000 ppm, or at levels greater than 1,000 ppm,or at levels greater than 100 ppm or at levels greater than 10 ppm or atdetectible levels. In embodiments, salts and solid of the invention donot contain sodium halide at levels greater than 10,000 ppm, or atlevels greater than 1,000 ppm, or at levels greater than 100 ppm or atlevels greater than 10 ppm or at detectible levels. In embodiments,salts and solid of the invention do not contain sulfate ions at levelsgreater than 10,000 ppm, or at levels greater than 1,000 ppm, or atlevels greater than 100 ppm or at levels greater than 10 ppm or atdetectible levels. In embodiments, salts and solids of the invention donot contain sodium ions greater than the amount that is added with theone or more organic additive that may be present, such as Na₂EDTA. Inembodiments, salts and solids of the invention do not contain sodiumions at levels greater than 10,000 ppm, or at levels greater than 1,000ppm, or at levels greater than 100 ppm or at levels greater than 10 ppmor at detectible levels.

In addition to using solid ferric iron-containing materials to producealkaline aqueous ferric iron salt solutions, the solid ferriciron-containing materials themselves may be useful in their solid formto treat reduced sulfur containing fluids. For instance, a solid ferriciron-containing material may be processed into particles (e.g.,impregnated into an inert substrate) that may be used as packing in acolumn for treating reduced sulfur-containing fluids.

iii. Composition

As noted above, the products resulting from the synthesis methods ofsections a.i and a.ii generally comprise (and in some instances, consistof, or consist essentially of) ferric iron, potassium, carbonate,bicarbonate, hydroxide, and optionally nitrate, optionally with one ormore organic additives. The compositions of such products are describedin greater detail below. For the purposes of this section, the term,“products” includes alkaline aqueous ferric iron salt solutions andsolid ferric iron-containing materials.

In one embodiment, a product comprises ferric iron (e.g., ferric ions)and one or more organic additives, where a molar ratio of the ferriciron to each of the organic additives is greater than 2.0. In thisregard, the molar ratio of the one or more organic additives to theferric iron may be sub-stoichiometric, meaning that the productcomprises more moles of iron than the organic additive. The use ofsub-stoichiometric amounts of organic additives relative to iron offerssignificant cost savings and other benefits. The method herein providessignificant cost improvements over existing technologies (e.g., LoCat,Streamline, Eco-Tec) that require utilizing organic additives, such aschelating agents that are present in stoichiometric equivalent amounts,or more frequently in a stoichiometric excess of the ferric iron. In yetanother embodiment, the molar ratio is at least 2.0. In anotherembodiment, the molar ratio is at least 3.0. In yet another embodiment,the molar ratio is at least 4.0. In another embodiment, the molar ratiois at least 5.0. In yet another embodiment, the molar ratio is at least7.5. In another embodiment, the molar ratio is at least 10. In yetanother embodiment, the molar ratio is at least 15. In anotherembodiment, the molar ratio is at least 50. In one embodiment, the molarratio is not greater than 1000. In another embodiment, the molar ratiois not greater than 100. Such above-described molar ratios applyindividually to any first organic additives, second organic additives,and so on and so forth that are present in the product.

The production of water soluble alkaline ferric iron solutions at pHabove 8.0 containing no or sub-stoichiometric ratios of organicadditives to ferric iron distinguishes the technology described hereinand offers significant cost savings and other advantages relative tocompeting H₂S control chemistries that use high ratios of organicadditives, such as chelating agents, to solubilize iron. Specifically,the alkaline ferric salts produced by these methods are believed to beinherently soluble in water or aqueous medium, and do not require highratios of expensive chelating agent to solubilize the iron at high pH.In embodiments, alkaline ferric salts produced by these methods arebelieved to self-assembled into ferric-carbonate complexes that areanionic in nature and that are inherently soluble in water or aqueousmedium, and do not require high ratios of expensive chelating agent tosolubilize the iron at high pH. It is believed that the majority offerric ions in the alkaline solutions described herein are not chelatedby organic chelating agents, and they are able to freely contact andreact with reduced sulfur compounds in a reduced sulfur-containingfluid. The ability to react directly with hydrogen sulfide and formferrous sulfide provides what is believed to be a novel and much moreefficient reaction pathway for capture and oxidation of hydrogensulfide. This reaction pathway is understood to capture the sulfur atomsfrom 1.5 hydrogen sulfide molecules for every iron atom. In contrast,competing H₂S control technologies that utilize 1:1 or higher ratios oforganic additives to iron ions must rely on indirect electron transferacross the organic chelating agents embedding the iron ions, which iskinetically slower and requires two iron ions to oxidize one H₂Smolecule. It is currently believed that the role of the low levels oforganic additives used in the technology described herein is to scavengerelatively low levels of free (i.e., non-complexed) ferric ions toprevent them from combining to form iron oxide particles. Because mostof the iron ions are at any moment are either complexed with sulfide (asiron sulfide, after H₂S capture) or complexed with carbonate,bicarbonate and potassium as a water-soluble ferric salt (beforehydrogen sulfide capture and after oxidative regeneration) there arebelieved to be few free ferric ions in solution, and hence little chanceto form ferric oxide particles. It is believed that trace or low-levelamounts of organic additives, as described herein, help scavenge lowlevels of free ferric ions, further reducing the possibility of ironparticle formation.

In one embodiment, a product comprises ferric iron (e.g. ferric ions)and one or more organic additives, where a molar ratio of the ferriciron to the organic additives, in total, is greater than 2.0. In yetanother embodiment, the molar ratio is at least 2.5. In anotherembodiment, the molar ratio is at least 3.0. In yet another embodiment,the molar ratio is at least 4.0. In another embodiment, the molar ratiois at least 5.0. In yet another embodiment, the molar ratio is at least7.5. In another embodiment, the molar ratio is at least 10. In yetanother embodiment, the molar ratio is at least 15. In anotherembodiment, the molar ratio is at least 50. In one embodiment, the molarratio is not greater than 1000. In another embodiment, the molar ratiois not greater than 100. Such above-described molar ratios also apply tothe sum of all organic additives present in the product.

In embodiments, of products herein, including solutions and solids, themolar ratio of the ferric iron to each of the one or more organicadditives is greater than 1, or at least 1.5, or at least 2, or at least2.5, or at least 3, or at least 4, or at least 5, or at least 7.5, or atleast 10, or at least 15, or at least 50; or between 1.1 and 50; orbetween 1.5 and 50; or between 2 and 50; or between 3 and 50; or between4 and 50; or between 5 and 50; or between 7.5 and 50; or between 10 and50; or between 15 and 50; or between 10 and 100; or between 50 and 100.

Suitable organic additives may comprise one or more functional groups,such as one or more hydroxyl groups, one or more carboxylic acid groupsand one or amino groups, among others. In one embodiment, an organicadditive is a polyol (i.e., an organic additive having at least twohydroxyl groups). In one embodiment, an organic additive is a sugaralcohol (i.e., having a chemical formula C_(n)H_(2n+2)O_(n)). In oneembodiment, an organic additive is a linear sugar alcohol, such as anyof the C3-C24 linear sugar alcohols. In one embodiment, an organicadditive is a sugar alcohol, where the sugar alcohol is sorbitol (e.g.,D-sorbitol, or L-sorbitol and combinations thereof). Other sugaralcohols that may be used include one or more of glycerol, erythritol,threitol, mannitol, galactitol, iditol, arabitol, ribitol, xylitol,volemitol, lactitol, maltotriitol, maltotetraitol, and polyglycitol. Anyof the D- or L-isomers of these compounds may be used, as well asmixtures thereof (e.g., racemic mixtures).

Other polyol organic additives that may be suitable includemonosaccharides, disaccharides, oligosaccharides and polysaccharides. Inone embodiment, an organic additive is a polysaccharide, where thepolysaccharide is pectin. Furthermore, extracts of plants, particularlyextracts of fruits, leaves or stems of fruits may be used as an organicadditive. For instance, an extract of fruit of the genus Prunus, or theleaves of the genus Prunus, or the stems of the genus Prunus andcombinations thereof may be used. The extracts of fruits, leaves and/orstems of other plants may similarly be used.

In one embodiment, an organic additive comprises at least one carboxylicacid group. In one embodiment, an organic additive comprises at leastone amino group. In one embodiment, an organic additive is anaminopolycarboxylic acid (i.e., having at least one amino group and atleast two carboxylic acid groups). In one embodiment, anaminopolycarboxylic acid is ethylenediaminetetraacetic acid (“EDTA”).While not being bound by any theory, it is believed thataminopolycarboxylic acids such as EDTA improve the rate of oxidation ofreduced alkaline iron salt solutions.

As noted above, the new alkaline aqueous ferric iron salt solutions maycomprise at least some nitrate ions (NO₃ ⁻). While not being bound byany theory, it is believed that nitrate anions may increase thesolubility of the ferric iron relative to the counter-ions of othercommercially available ferric salts (e.g., ferric chloride, ferricsulfate). Furthermore, nitrate ions may have additional benefits, suchas being less corrosive than other ions (e.g., halides) to steel,aluminum and other materials that may be exposed to the alkaline aqueousferric iron salt solutions during commercial operation. In oneembodiment, a product comprises a molar ratio of nitrate to ferric ironof at least 1.0. In another embodiment, a product comprises a molarratio of nitrate to ferric iron of at least 1.2. In yet anotherembodiment, a product comprises a molar ratio of nitrate to ferric ironof at least 1.5. In another embodiment, a product comprises a molarratio of nitrate to ferric iron of at least 2.0. In yet anotherembodiment, a product comprises a molar ratio of nitrate to ferric ironof at least 2.5. In another embodiment, a product comprises a molarratio of nitrate to ferric iron of at least 3.0.

The alkaline aqueous ferric iron salt solution as a concentrate or indiluted form does not corrode iron or carbon steel.

As noted above, the new alkaline aqueous ferric iron salt solutionsgenerally comprise at least some potassium (K⁺). While not being boundby any theory, it is believed that potassium cations increase thesolubility of the ferric iron-carbonate complex, and may act ascounter-ions to the negatively charged ferric iron-carbonate complexes.In one embodiment, a product comprises a molar ratio of potassium toferric iron of at least 1.0. In another embodiment, a product comprisesa molar ratio of potassium to ferric iron of at least 2.0. In yetanother embodiment, a molar ratio of potassium to ferric iron of atleast 3.0. In another embodiment, a product comprises a molar ratio ofpotassium to ferric iron of at least 4.0. In yet another embodiment, amolar ratio of potassium to ferric iron of at least 5.0. In anotherembodiment, a product comprises a molar ratio of potassium to ferriciron of at least 6.0. In yet another embodiment, a product comprises amolar ratio of potassium to ferric iron of at least 7.0. In yet anotherembodiment, a product comprises a molar ratio of potassium to ferriciron of at least 9.0. In yet another embodiment, a product comprises amolar ratio of potassium to ferric iron of at least 10. In yet anotherembodiment, a product comprises a molar ratio of potassium to ferriciron of at least 12.

In concentrates of the alkaline ferric iron salt solutions herein theratio of potassium ion to ferric ion ranges from 6 to 11 and morepreferably 6.6 to 12. In a specific embodiment, the ratio of potassiumion to ferric ion in the solution concentrates ranges from 8.5 to 9.5 orfrom 8.9 to 9.1. In an embodiment, the ratio of potassium ion to ferricion in the solution concentrates is 9.

In solutions prepared by dilution of solution concentrates, which areworking solutions used to scrub reduced sulfur compounds from fluids, inembodiments, the ratio of potassium ion to ferric ion is generally veryhigh largely because concentrates are typically diluted using potassiumcarbonate/bicarbonate buffers. For example, in diluted workingsolutions, the ratio of potassium ion to ferric ion can be greater than20, or greater than 50 or greater than 75, or greater than 100. Inspecific diluted working solutions, the ratio of potassium ion to ferricion is 65 or 95.

Unlike other liquid redox technologies used to scrub reduced sulfurcompounds from fluids the aqueous alkaline ferric iron salt solutionsdescribed herein do not produce any detectable sulfate when oxidized,and do not lose alkalinity during multiple H₂S capture-regenerationcycles. In laboratory tests, samples of the aqueous alkaline ferric ironsalt solutions that had undergone repeated H₂S capture/regenerationcycles were neutralized to pH 7 and tested with Quantofix sulfate teststrips (Machery-Nagel, Duren, Germany). No evidence of sulfate wasobserved (<200 mg/L). In addition, repeated H₂S capture regenerationcycles, even in the presence of 40% CO₂ gas streams, did not result ingradual loss of alkalinity, as would be expected if sulfate orthiosulfate was produced during sulfide oxidation. During a 7-monthpilot project utilizing the same 70 liter batch of the aqueous alkalineferric iron solution observed pH's never dropped below 8.5. It appearsthat virtually all captured sulfide is in the aqueous alkaline ferriciron solutions described herein is converted to elemental sulfur, notsulfate or thiosulfate.

The absence of sulfate/thiosulfate production and retention ofalkalinity by the aqueous alkaline ferric iron complex described hereinare major advantages over competing liquid redox processes for H₂Sremoval. While not bound by any theory it is believed that the directreaction of reduced sulfur compounds with the ferric iron-carbonatecomplex to form iron sulfide immediately removes virtually all capturedsulfide ions from the solution, which in turn prevents the formation ofsulfate and loss of alkalinity during oxidative regeneration. In LoCatand similar liquid redox technologies sulfide is initially captured byan alkaline buffer, with no direct conversion to iron sulfide. Thecaptured sulfide ions are partially oxidized to sulfate and thiosulfateduring regeneration. As a result, the solution gradually losesalkalinity and requires a regular purge stream to remove the accumulatedsulfate, as well as regular addition of sodium hydroxide or other basesto retain alkalinity. In embodiments, the aqueous alkaline ferric ironsalt solutions described herein, when used to scrub fluids containingreduced sulfur compounds (particularly H₂S), do not produce anydetectable sulfate when oxidized, and do not lose alkalinity duringmultiple H₂S capture-regeneration cycles. In embodiments, the level ofsulfate produced in the aqueous alkaline ferric iron salt solutions whenused in such scrubbing applications is less than 500 mg/L. Inembodiments, the level of sulfate produced in the aqueous alkalineferric iron salt solutions when used in such scrubbing applications isless than 400 mg/L. In embodiments, the level of sulfate produced in theaqueous alkaline ferric iron salt solutions when used in such scrubbingapplications is less than 300 mg/L. In embodiments, the level of sulfateproduced in the aqueous alkaline ferric iron salt solutions when used insuch scrubbing applications is less than 200 mg/L.

c. Methods of Using Alkaline Aqueous Ferric Iron Solutions

As noted above, the alkaline aqueous ferric iron salt solutions of thepresent invention may be used to treat reduced sulfur-containing fluids.For instance, the new alkaline aqueous ferric iron salt solutions may beused to treat natural gas streams, biogas streams (e.g., fromwastewater, landfills, among others), oil, geothermal vent gas andeffluents from paper mills, among others. Furthermore, the new alkalineaqueous ferric iron salt solutions may be used to treat the effluentfrom an amine process where the effluent is predominately comprised ofacid gases (CO₂ and H₂S). The solid ferric iron-containing materialsdescribed herein may also be useful for treating these types of reducedsulfur-containing fluids.

With reference now to FIG. 1, an embodiment of a method (100) fortreating a reduced sulfur-containing fluid is shown. As shown, themethod (100) generally comprises first contacting an alkaline aqueousferric iron solution with a reduced sulfur-containing fluid (110). Thealkaline aqueous ferric iron solution comprises ferric ions (Fe³⁺),potassium ions (K⁺), carbonate ions (CO₃ ²⁻) and bicarbonate ions (HCO₃⁻), optionally with one or more organic additives. The reducedsulfur-containing fluid generally comprises at least some of at leastone reduced sulfur compound, such as H₂S.

As used herein, “reduced sulfur compound” means any sulfur compoundhaving an oxidation state of −2. For instance, hydrogen sulfide (H₂S) isa compound where the oxidation state of the sulfur is −2. Other reducedsulfur compounds include carbonyl sulfide (COS), carbon disulfide (CS₂)and mercaptans. Oxidized forms of sulfur that may be produced using thealkaline aqueous ferric iron solutions of the present invention includeelemental sulfur, which has an oxidation state of 0.

Concomitantly with the contacting (110), the method generally comprisesproducing a reduced alkaline iron solution or suspension of reduced ironparticles, e.g., ferrous sulfide (FeS) or related iron sulfides (120).The producing step (120) generally comprises oxidizing at least some ofthe at least one reduced sulfur compounds via the alkaline aqueousferric iron solution, thereby reducing at least some of the ferric ionsto ferrous ions. The oxidation-reduction reaction generally convertsreduced sulfur compounds such as H₂S to ferrous sulfide or elementalsulfur, for instance. Furthermore, the producing step (120) generallycomprises producing at least some iron sulfide compounds. While notbeing bound by any theory, the resulting ferrous ions (Fe²⁺) areunderstood to ultimately react with the reduced sulfur compounds to formferrous sulfide (e.g., FeS), which is a black precipitate.

Generally, concomitantly to the contacting step (a, 110) and producingstep (b, 120), the method (100) comprises discharging a purified fluidcontaining little or no reduced sulfur compounds. In other words, thepurified fluid (outlet fluid) has a substantially lower concentration ofreduced sulfur compounds than the reduced sulfur-containing fluid (inletfluid). For instance, an inlet natural gas stream or inlet biogas gasstream containing H₂S may be discharged as a purified gas stream havinga substantially reduced H₂S concentration. In this regard, it has beenfound in laboratory and pilot tests that the alkaline aqueous ferriciron salt solutions of the present invention can reduce highconcentrations of H₂S (e.g., as high as 100,000 ppm) to non-detectablelevels. Other “liquid redox” H₂S control technologies that use 1:1 orhigher ratios of chelating agents to ferric iron have trouble reducingH₂S to less than 10 ppm in part because the electron transfer processbetween iron and sulfide is believed to be indirect, through the organicchelating agent. In contrast the current invention is believed to allowimmediate and direct reaction between ferric iron and hydrogen sulfide,forming ferrous sulfide.

After or concomitantly with the contacting (110) and producing (120)steps, the method generally comprises exposing the reduced alkaline ironsolution or suspension of ferrous sulfide particles to an oxidizingagent (130). Suitable oxidizing agents may include oxygen (e.g., in air)and hydrogen peroxide, among others. The exposing step (130) therebyproduces a regenerated alkaline aqueous ferric iron salt solution.Furthermore, this step generally comprises producing at least someelemental sulfur (e.g., from the ferrous sulfide formed in the producingstep (120)). Thus, the regenerated alkaline aqueous ferric iron solutionis generally a mixture of solid elemental sulfur and the alkalineaqueous ferric iron solution. The contacting (110), producing (120) andexposing (130) steps may be repeated at least one time. Due to thereduced alkaline aqueous ferric iron solution's ability to beregenerated back into an alkaline aqueous ferric iron salt solution, ithas been found that these steps may be repeated indefinitely.

In addition, elemental sulfur can periodically or continuously beseparated (140) from the regenerated alkaline iron solution.

Unexpectedly, the inventors have found that performing the contacting(110), producing (120) and exposing steps (130) on an alkaline aqueousferric iron solution that comprises at least some iron oxide-basedparticles may be beneficial for reducing the concentration of suchiron-based particles. For instance, it has been found that theiron-based particles may be reduced or eliminated completely via thesesteps (110, 120 and 130). Thus, in one embodiment, prior to thecontacting step (110), an alkaline aqueous ferric iron solutioncomprises at least some iron-based particles, and due to the contactingstep (110), producing step (120) and the exposing step (130), theregenerated alkaline aqueous ferric iron solution has a reducedconcentration of iron-based particles (e.g., free of iron-basedparticles). It is believed that hydrogen sulfide may attack the ironoxide particles and upon oxidation they revert to the soluble aqueousalkaline ferric iron salt.

In some embodiments, the contacting step (110), producing step (120) andexposing step (130) occur concomitantly. For instance, a scrubbingcolumn utilizing an alkaline aqueous ferric iron salt solution may becontacted with a reduced sulfur-containing fluid and exposed to anoxidizing agent concomitantly. An example of where this might be usefulis for odor control (e.g., in the production of paper or municipalwastewater treatment). Odiferous fluids containing reduced sulfurcompounds such as H₂S that are not present in a concentration sufficientto be a combustion hazard may be combined with an oxidizing fluid suchas air. The resulting gas mixture may be passed through a scrubbingcolumn. A similar process may be used in the treatment of an acid gaseffluent from an amine process, which may be low in combustiblehydrocarbons. These examples differ from natural gas stream or biogasstream where there is a safety concern of adding an oxidant (e.g., O₂)to a combustible fluid (e.g., methane).

As noted above, elemental sulfur is produced via the method (100). Thus,the method (100) generally produces a solid-liquid mixture, where theliquid component is an alkaline aqueous ferric iron salt solution, andthe solid component comprises (or consists essentially of) elementalsulfur. Thus, the solid elemental sulfur may be separated from thealkaline aqueous ferric iron solutions via any suitable solid-liquidseparation technique. For instance, the solid elemental sulfur may bereadily separated from the regenerated alkaline aqueous ferric ironsolution by passing the solid-liquid mixture through a barrier that isat least partially impenetrable by the elemental sulfur, such as a sieveand/or filter. Additional separations may be employed to further purifythe elemental sulfur and/or recover the alkaline aqueous ferric ironsolution. For instance, the sulfur-rich solid-liquid mixture may beheated under pressure to form elemental sulfur, which readily separatesfrom the alkaline aqueous ferric iron salt solution. Furthermore, thesulfur-rich solid-liquid mixture may be separated via froth flotation.

With reference to FIG. 2, an exemplary system (200) of the invention forremoving a reduced sulfur compound, such as H₂S, from a reduced sulfurcompound-containing fluid is schematically illustrated. A reservoir alsotermed a primary accumulator (205) is provided for holding the alkalineaqueous ferric iron solution (scrubber solution). It is also to thisprimary accumulator (205) that regenerated scrubber solution is returnedafter regeneration.

Scrubber solution is pumped, e.g., via centrifugal or displacement pump(206), to scrubber column (210, also termed a contactor) through fillconduit (207). Scrubber solution is introduced to the scrubber column(210), for example, through a plurality of sprayers (208). The scrubbercolumn (210) is optionally provided with filler (211), preferably ahigh-surface area filler, (e.g., column packing, such as random columnpacking) to enhance contact between the fluid to be scrubbed and thescrubber solution. In an embodiment, scrubber solution cascadesdownward, via gravity, through the filler (211). The fluid to bescrubbed, illustrated as a gas containing reduced sulfur compound, suchas biogas, is introduced into the scrubber column via inlet conduit(221) though a gas inlet (220) which facilitates dispersal of thereduced sulfur-containing gas into the scrubber column in contact withscrubber solution. Scrubbed gas from which reduced sulfur compound(s)have been removed exits the scrubber column (210) via gas outlet conduit(222). The flow rate of reduced sulfur-containing gas and scrubbersolution into the scrubber column is adjusted to decrease the reducedsulfur compound level(s) in the gas to a desired level. In anembodiment, at least 98% (v/v) of the reduced sulfur compound can beremoved from the reduced sulfur-containing fluid. In an embodiment, atleast 98% (v/v) of H₂S present can be removed from the reducedsulfur-containing fluid. In an embodiment, at least 99% (v/v) of H₂Spresent can be removed from the reduced sulfur-containing fluid. Inmultiple laboratory and pilot tests H₂S removal was greater than 99.9%

Ferric iron in the scrubber solution is at least partially reduced toferrous iron on contact with the reduced sulfur-containing fluid. Inaddition, after contact with the reduced sulfur-containing fluid, the atleast partially reduced scrubber solution contains sulfur, particularlyin the form of iron sulfide and more particularly as FeS. The at leastpartially reduced scrubber solution may also contain precipitatedelemental sulfur. At least partially reduced scrubber solution includingiron sulfide and any precipitated elemental sulfur is pumped from thesump region (213) of the scrubber column (210) through sump conduit(214) to regeneration tank (230) via sump pump (216, e.g., a centrifugalpump). Ferrous iron is oxidized to ferric iron and elemental sulfur isformed in the regeneration tank (230). The regeneration tank is providedwith an air inlet (231) to provide oxygen for regeneration of the atleast partially reduced scrubber solution to form elemental sulfur. Airis optionally dispersed into the at least partially reduced scrubbersolution via one or more dispersers (232, e.g., gas spargers).

Elemental sulfur formed on regeneration (i.e., via the oxidation by air)floats to the top of the liquid in the regeneration tank (230) andspills into weir (234) provided for collection of elemental sulfur and aportion of the regenerated scrubber solution (elemental sulfur-richregenerated scrubber solution). Regenerated scrubber solution withoutelemental sulfur is collected from the regeneration tank via collectionconduit (239), for example by gravity flow, and returned to the primaryaccumulator (205). Sulfur-rich regenerated scrubber solution may bepassed through a bubble trap (235) to remove entrained gas and iscollected in the sulfur-rich accumulator (240). Collected sulfur-richregenerated scrubber solution is passed to sulfur filter (242) whereelemental sulfur is separated from regenerated scrubber solution and iswashed via wash water feed (243). The separated regenerated scrubbersolution is collected in accumulator (244) and pumped through returnconduit (247) via return pump (246) to primary accumulator (205).Separated sulfur that has been substantially dried is passed to the drysulfur accumulator (250).

The system as illustrated is typically operated continuously with aselected flow of scrubber solution and reduced sulfur-containing fluidinto the scrubber column (210) to achieve the desired level of reducedsulfur removal. At least partially reduced scrubber solution iscontinuously conveyed to the regenerator tank and regenerated scrubbersolution is returned to the primary accumulation tank. In theillustrated system, sulfur filtration is performed periodically in abatch-wise mode when a preselected amount of elemental sulfur hasaccumulated. The illustrated scrubber column (210) is one example of anumber of known means for contacting a scrubber solution with a fluid.For instance, other means for contacting a scrubber solution with areduced sulfur-containing fluid include fluid filled contactors (i.e.,absent filler (211)), static mixers and Venturi systems. One of ordinaryskill in the art can readily choose an appropriate known contactorconfiguration for a given application for removal of reduced sulfur froma given fluid.

d. Miscellaneous

As noted above, the alkaline aqueous ferric iron salt solutions of thepresent invention exhibit important advantages over the prior art. Forinstance, the alkaline aqueous ferric iron salt solutions may beproduced via various methods that reduce costs, and alkaline aqueousferric iron solutions may be used in an H₂S capture-oxidativeregeneration cycle to treat reduced sulfur-containing fluids. Anadditional advantage is that the alkaline aqueous ferric iron solutionsmay be at least partially frozen and then thawed without negativelyimpacting the ability of the solution to treat reduced sulfur-containingfluids. Although crystallization of the solution may occur at lowtemperatures (e.g., 1-5° C.), upon heating to room temperature thecrystals dissolve, reconstituting the active alkaline aqueous ferriciron salt solutions. Thus, alkaline aqueous ferric iron salt solutionsmay be stored from minus 20° C. to 55° C. without the need fortemperature regulation. This differs from technologies that utilizeparticles suspended in a solution (e.g., iron oxide slurries) that maynot recover their ability to treat reduced sulfur-containing fluidsafter heating or a single freeze-thaw cycle.

When a Markush group or other grouping is used herein, all individualmembers of the group and all combinations and sub-combinations possibleof the group are intended to be individually included in the disclosure.Every formulation or combination of components described or exemplifiedcan be used to practice the invention, unless otherwise stated. Specificnames of compounds are intended to be exemplary, as it is known that oneof ordinary skill in the art can name the same compounds differently.

One of ordinary skill in the art will appreciate that methods, includingpreparation methods and analytical methods, materials and device andsystem elements other than those specifically exemplified can beemployed in the practice of the invention without resort to undueexperimentation. All art-known functional equivalents of any suchmethods or materials are intended to be included in this invention.

Whenever a range is given in the specification, for example, acomposition range, a range of process conditions, a range of pressuresor temperatures or the like, all intermediate ranges and sub-ranges, aswell as all individual values included in the ranges given are intendedto be included in the disclosure. All ranges listed in the disclosureare inclusive of the range endpoints listed.

The invention illustratively described herein suitably may be practicedin the absence of any element or elements, limitation or limitationsthat is not specifically disclosed herein.

Without wishing to be bound by any particular theory, there can bediscussion herein of beliefs or understandings of underlying principlesor mechanisms of action relating to the invention. It is recognized thatregardless of the ultimate correctness of any mechanistic explanation orhypothesis, an embodiment of the invention can nonetheless be operativeand useful.

All references throughout this application, for example patent documentsincluding issued or granted patents or equivalents; patent applicationpublications; and non-patent literature documents or other sourcematerial; are hereby incorporated by reference herein in theirentireties, as though individually incorporated by reference.

Sengupta AK and Nandi AK (1974) “Complex Carbonates of Iron (III) Z,anorg. Allg. Chem., 403, 327-336 and references cited therein are eachincorporated by reference herein in its entirety for description ofcomplex carbonate salts of Fe(III) and certain water-soluble salts ofFe(III). The reference also includes descriptions of the synthesis ofthe salt K₆[Fe₂(OH)₂(CO₃)₅]. H₂O and methods of identifying andcharacterizing such salts, by U.V./visible spectroscopy and Infraredspectroscopy, among others. The reference includes visible spectra(Figure. 1, therein) of 1.198 mg Fe³⁺ in KHCO₃ solution (35%) whichexhibits a maximum absorbance at 460 nm. The description of such methodsand the characterization of salts is incorporated by reference herein.

All patents and publications mentioned in the specification areindicative of the levels of skill of those skilled in the art to whichthe invention pertains. References cited herein are incorporated byreference herein in their entirety to indicate the state of the art, insome cases as of their filing date, and it is intended that thisinformation can be employed herein, if needed, to exclude (for example,to disclaim) specific embodiments that are in the prior art. The termsand expressions which have been employed are used as terms ofdescription and not of limitation, and there is no intention in the useof such terms and expressions of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of theinvention claimed. Thus, it should be understood that although thepresent invention has been specifically disclosed by preferredembodiments and optional features, modification and variation of theconcepts herein disclosed may be resorted to by those skilled in theart, and that such modifications and variations are considered to bewithin the scope of this invention.

THE EXAMPLES Example 1

A panel of experiments was performed using a variety of ferric salts andalkali metal bases. Pairwise combinations of (1) dry powders of theferric salts (FeCl₃, Fe₂(SO₄)₃.XH₂O and Fe(NO₃)₃.9H₂O) and (2) thealkali metal bases (NaOH, KOH, Na₂CO₃, K₂CO₃, NaHCO₃, and KHCO₃) wereplaced in test tubes. The alkali metal bases were added in a ratio of6.8 to 1 with respect to the moles of alkali metal to the moles of iron.Approximately 5 mL of water was added to each test tube and each testtube was shaken to completely mix the water with the ferric salt andalkali metal base. In the case of alkali metal carbonates, a vigorousreaction with CO₂ production occurred. The resulting mixture for eachexperiment was then visually observed for presence of particles (e.g.,iron oxide particles). The results of the panel of experiments aresummarized in Table 1, below. A designation of “PPT” indicates thatprecipitates were observed in the resulting mixture.

TABLE 1 Base Chemicals used and the K₂CO₃ + level of their purity. NaOHKOH Na₂CO₃ K₂CO₃ NaHCO₃ KHCO₃ KHCO₃* FeCl₃ (anhydrous) PPT PPT PPT PPTPPT PPT PPT Fe₂(SO₄)3•9H₂O PPT PPT PPT PPT PPT PPT PPT Fe(NO₃)3•9H₂O PPTPPT PPT Soluble PPT PPT PPT *Approximately 2 moles of bicarbonate saltswere used for each mole of carbonate salts, to maintain comparablealkali metal concentrations.

As shown above in Table 1, the only combination that resulted in a fullysoluble mixture upon initial mixing was the Fe(NO₃)₃.9H₂O and K₂CO₃pair.

Example 2

An alkaline aqueous ferric iron salt solution was manufactured by firstpreparing a solid mixture having 213.7 g of ferric nitrate nonahydrate(Fe(NO₃)₃.9H₂O), 250 g of anhydrous potassium carbonate (K₂CO₃) and 9.62g of D-sorbitol. The solid mixture was placed in a beaker with amagnetic stir bar on a magnetic stir plate. While stirring, 793 mL of anaqueous solution having 19.7 g of the disodium salt of EDTA was added tothe beaker. The addition of the water resulted in a vigorous reactionthat released CO₂ gas. The alkaline aqueous ferric iron salt solutionwas diluted using an aqueous potassium carbonate-bicarbonate buffer at aratio of 1:25 alkaline aqueous ferric iron salt solution to aqueouspotassium carbonate-bicarbonate buffer by adding the alkaline aqueousferric iron solution into the aqueous potassium carbonate/bicarbonatebuffers. The exemplary buffer solution used to dilute the concentratedferric iron solutions was a 50:50 (vol:vol) mixture of 0.9 M aqueousK₂CO₃ and 1.8 M KHCO₃ at pH 10.1. Useful ferric iron solutions can beprepared by dilution of the concentrated solution with potassiumcarbonate-bicarbonate buffer. Useful ferric iron solutions can beprepared by dilution of the concentrated solution with potassiumcarbonate-bicarbonate buffer where the dilution is 1:1 (vol/vol) up to1:60 (vol:vol) concentrate:buffer.

Concentrate of the alkaline aqueous ferric iron solutions is stable forat least one year for use in preparation of working solutions byappropriate dilution (e.g., a 1:20 dillution with buffer)

Afterwards, the diluted alkaline aqueous ferric iron solution was usedto scrub hydrogen sulfide from a hydrogen sulfide containing gas. Aftercapturing the hydrogen sulfide gas, the alkaline aqueous ferric ironsolution was regenerated by sparging room temperature air through thesolution, thereby producing solid sulfur and regenerating the ferriciron salt solution. Solid sulfur was removed from the mixture by passingthe sulfur-alkaline aqueous ferric iron solution over a 25-micrometerscreen. The capture-regeneration cycle was repeated numerous times,resulting in an average of over 100 hydrogen sulfide molecules beingcaptured and oxidized for every iron atom in the original mixture withno apparent loss of H₂S capture or regeneration activity over the courseof the experiment.

Example 3

Preferred Mole Ratios of Potassium and Ferric Iron and Organic Additivesin Concentrated and Dilute Working Solutions

Various mole ratios of potassium, sorbitol, EDTA and ferric iron weretested to determine short and long term solubility of concentratedaqueous alkaline iron solutions, with the goal of determining preferredmole ratios that maintain high solubility. In these experiments drysolids of all chemicals were mixed and deionized water (10 mL) was addedto the mixed solids. All test samples contained 1.3465 g ofFe(NO₃)₃.9H₂O, which resulted in a final molarity of 0.278 M Fe(NO₃)₃.Potassium carbonate, D-sorbitol and Nae-EDTA were added as needed toachieve the mole ratios listed in the Table 2. Upon addition of water tothe dry solids a vigorous reaction occurred and either a clear, dark,fully soluble solution or a solution with precipitate of iron oxideparticles resulted.

The results of these tests are listed in Table 2. In the absence ofsorbitol and EDTA (samples 1-4 in Table 2 below) fully soluble aqueousalkaline ferric iron solutions occurred at K:Fe mole ratios of 9:1 and12:1, but substantial precipitation of iron oxide particles occurred atlower K:Fe mole ratios (4:1 and 6.6:1). The 9:1 and 12:1 K:Fe solutionsremained clear and soluble for 4-5 days but then precipitated after oneweek. However 1:20 dilutions of the 9:1 and 12:1 K:Fe concentrates witha potassium carbonate-bicarbonate buffer (0.9M KHCO₃:0.45M K₂CO₃)remained fully soluble. The K:Fe mole ratios of these dilute solutionsare much higher, 138:1 and 141:1 for the diluted 9:1 and 12:1concentrates, respectively. These results demonstrate that at K:Fe moleratios >8 the aqueous alkaline ferric iron solutions described hereinare inherently highly soluble even in the absence of organic additives.This is a highly unusual result for ferric iron compounds, which arenormally virtually insoluble at pH's above 5-6.

In the presence of D-sorbitol and EDTA at 1:10 mole ratios relative toferric iron (samples 5-8) somewhat different results occurred. The6.6:1, 9:1 and 12:1 K:Fe concentrated solutions were fully water solubleand remained so for at least 7 days, while the 4:1 K:Fe testprecipitated immediately. 1:20 dilutions of these soluble concentratesinto the same potassium carbonate-bicarbonate buffer described aboveremained fully soluble as well. It should be noted that the dilutesolutions with high K:Fe ratios described herein are the “workingsolutions” of aqueous, alkaline ferric salts that are used to scrubhydrogen sulfide and other reduced sulfur compounds from gas streams.Exemplary working solutions are made by diluting concentrates such asthose listed in Table 2 with potassium carbonate-bicarbonate buffer(0.9M KHCO₃:0.45M K₂CO₃) at 1:10, 1:20 or 1:30 dilution ratios.

TABLE 2 K:Fe Sorbitol:Fe EDTA:Fe Solution after Solution after Solutionafter Sample Mole ratio Mole ratio Mole ratio mixing 1 day 1 week 1 4:10 0 PPT PPT PPT 2 6.6:1  0 0 PPT PPT PPT 3 9:1 0 0 Fully Fully PPTsoluble, dark soluble, dark brown brown 4 12:1  0 0 Fully Fully PPTsoluble, dark soluble, dark brown brown 5 4:1 1:10 1:10 PPT PPT PPT 66.6:1  1:10 1:10 Fully Fully Fully soluble, dark soluble, dark soluble,dark brown brown brown 7 9:1 1:10 1:10 Fully Fully Fully soluble, darksoluble, dark soluble, dark brown brown brown 8 12:1  1:10 1:10 FullyFully Fully soluble, dark soluble, dark soluble, dark brown brown brown

Example 4

Purification of Mixed Metal Salts from Aqueous Alkaline Ferric SaltSolutions.

Using an 80:20 acetone-water mixture as an extractant, we concentratedand purified various mixed metal salts from concentrated aqueousalkaline ferric salt solutions. In general, a given volume ofconcentrated aqueous alkaline ferric salt solution was sequentiallyextracted with a 10× volume of 80:20 acetone-water. With eachextraction, a reduced volume of viscous, darkly colored, fullywater-soluble ferric iron solution was formed below the acetone-waterlayer. The acetone-water layer was then removed, the separated layer offerric iron solution was made up to its original volume by addition ofdeionized water, and then the acetone-water extraction was repeated. Thefinal volume of purified aqueous alkaline ferric iron salt solution wasmade up to its original volume by addition of deionized water and thepurified ferric iron salt sample and the acetone-water extractions wereanalyzed for total iron, potassium, sodium, nitrate, andcarbonate/bicarbonate. A sample of a concentrate of the aqueous alkalineferric salt solution was also analyzed.

The concentrate of the alkaline ferric iron solution which was purifiedhad the following composition:

Iron: 32,600 mg/L/0.58 M

Potassium: 133,000 mg/L/3.41 M

Sodium: 4,050 mg/L/0.176 M

Nitrate: 14,700 mg/L/0.245 M

Carbonate: 7.4 mg/L

Bicarbonate: 104,000 mg/L

After one 10× acetone-water extraction of the concentrate solutionabove, the slightly purified ferric iron solution contained:

Iron: 28,400 mg/L/0.507 M

Potassium: 55,300 mg/L/1.42 M

Sodium: 2,720 mg/L/0.118 M

Nitrate: 2,520 mg/L/0.042 M

Carbonate: 4.4 mg/L

Bicarbonate: 67,200 mg/L

The potassium to ferric iron mole ratio in the once-purified ferriccomplex is 2.8 to 1, suggesting a K₃Fe-carbonate complex, or aK₆Fe₂-carbonate complex. The bicarbonate to ferric iron mole ratio is2.17, although this value is likely low due to limitations of thebicarbonate analysis.

After three sequential 10× acetone-water extractions the purified ferriciron solution contained:

Iron: 23,200 mg/L/0.414 M

Potassium: 38,700 mg/L/0.992 M

Nitrate: Not detected

The potassium to ferric iron mole ratio is 2.4 to 1. This is stillsuggestive of K₃Fe or K₆Fe₂ mixed metal carbonate complexes, but less sothan the previous result. It is possible that the complexes are K₂Fe orK₄Fe₂ or K₅Fe₂ mixed metal carbonate complexes.

The disappearance of nitrate after three sequential extractions suggeststhat nitrate is not part of the mixed metal ferric iron complex(es). Thenitrate has apparently been removed in the extractions. Carbonate andbicarbonate were not tested in this analysis but are clearly shown to bepresent by reaction of the purified solution with 8M hydrochloric acidwhich results in significant bubbling, indicating release of CO₂.

These results indicate that potassium, ferric iron and bicarbonate arepart of the purified compound. There is approximately three times asmuch potassium as ferric iron in the purified complex. There is at leasttwice as much bicarbonate as ferric iron in the complex. Nitrate doesnot appear to be present. A small amount of sodium is present, but itcannot be determined if sodium is present in the complex. We note thatthere may be more than one complex in the purified material.

Example 5

An alkaline aqueous ferric iron salt solution was prepared using 1.3465g of ferric nitrate nonahydrate, 1.5755 g of potassium carbonate, 0.0605g of D-sorbitol, and 0.124 g of Nae-EDTA. The molar ratios of theorganic additives (D-sorbitol and Na₂EDTA) were each 1:10 relative toferric iron. After the production of the alkaline aqueous ferric ironsalt solution, a purified ferric iron salt solution was obtained in amanner consistent to Example 4 using an acetone-water mixture (80-20(v/v) solution). Two serial extraction steps were performed on thealkaline aqueous ferric iron salt solution. Purities and sources of thematerials used in this procedure are provided in Table 3.

TABLE 3 Material Source Purity Ferric nitrate nonahydrate CarolinaBiological High purity reagent grade Potassium carbonate CarolinaBiological Reagent grade D-Sorbitol Sigma-Aldrich >=98 wt. % Disodiumsalt, EDTA Carolina Biological Reagent grade Potassium bicarbonateCarolina Biological Reagent grade Dowex 21K chloride Sigma-Aldrich N/Aanion exchange resin Amberlite IR120 sodium Sigma-Aldrich N/A cationexchange resin Acetone Carolina Biological 99.5 wt. %

Four glass sample vials (two experimental vials and two control vials)were packed with ¼-inch beds of ion exchange resin. Two of the vialswere packed with Dowex 21K (Cl⁻) anion exchange resin and the other twovials were packed with Amberlite IR120 (Na⁺) cation exchange resin.

After packing the vials with the ion exchange resins, the experimentalvials were prepared as follows. One vial of cation exchange resin andone vial of anion exchange resin were charged with 3 mL of 1.8 Mpotassium bicarbonate buffer solution. After approximately 5 minutes,the excess fluid was decanted from the ion exchange resin beads. The ionexchange resin beads were then rinsed with distilled water to removeexcess buffer solution and suspended in 0.45M potassium bicarbonatebuffer. After suspending in buffer, the excess buffer was decanted offand 200 microliters of the purified ferric iron salt solution was addedto each of the experimental vials. The experimental vials were thendecanted approximately 2 minutes later to remove the excess liquid fromthe vials. After decanting, a 0.45 M potassium bicarbonate buffersolution was added to the experimental vials to thoroughly rinse the ionexchange resins to remove any unbound ferric iron salt.

After packing the vials with the ion exchange resins, the control vialswere prepared as follows. One of each cation exchange resin and anionexchange resin was suspended in distilled water. The control vials werethen decanted approximately 2 minutes later to remove the excess liquidfrom the vials. After decanting, a 0.45 M potassium bicarbonate buffersolution was added to the control vials to thoroughly rinse the ionexchange resins.

After washing both the experimental vials and control vials with the0.45 M buffer solution, the experimental cation exchange resin wasidentical in color (bronze) to the control sample of the cation exchangeresin. Conversely, the anion exchange resin treated with the purifiedmixed metal ferric salt was a deep amber color, similar in color to thepurified alkaline ferric iron salt solution. Furthermore, the controlanion exchange resin sample had a light brown color. The significantlydarker color of the anion exchange resin compared to control anionexchange resin indicates binding of negatively charged (anionic) ferricspecies from the isolated ferric iron salt solution. In contrast, thelack of a significant difference in color between treated and controlcation exchange resin, respectively, indicates no significant binding ofcationic ferric species.

It is assumed with high confidence that the ferric iron complex, whetheranionic or cationic in nature, is responsible for the dark amber colorfound in solutions described herein. Thus, since no color change wasobserved with the experimental cation exchange resin relative to thecontrol, it is believed that the ferric iron complex of the solutionsdescribed herein is not cationic in nature. In contrast, the colorchange of the anion exchange resin to a dark amber color demonstratesthat the ferric ion complex of the solutions described herein isnegatively charged, i.e., the ferric complex is an anion. This anionicferric iron complex is believed to be critical to the unusual solubilityof the ferric iron at high pH (>8) and its direct reactivity withreduced sulfur compounds (e.g., H₂S) in reduced sulfur-containingfluids. Conversely, positively charged ferric ions are virtuallyinsoluble at pH greater than 6.

In sum, the ability to create and use thermodynamically stable, fullyaqueous soluble, negatively charged ferric iron complexes may create awide range of potential industrial applications in addition to thispatent application's focus on the treatment of reduced sulfur-containingfluids.

Example 6

A Thermo Scientific UV-VIS spectrophotometer was used to obtain a UV-Visspectrum of a sample of purified aqueous alkaline ferric iron saltsolution. The sample used in the analysis was prepared by firstproducing a concentrated aqueous alkaline ferric iron salt solution from1.3465 g of ferric nitrate nonahydrate, 1.5755 g of potassium carbonate,0.0605 g of D-Sorbitol, and 0.124 g of Nae-EDTA. The mole ratios ofD-sorbitol and EDTA relative to ferric iron are each 1:10. From thisconcentrate, the purified ferric iron salt solution was purified byextraction in a manner consistent with Example 4. Two serial extractionswere performed using a 1:10 ratio of concentrated aqueous alkalineferric iron salt solution to an 80:20 (v/v) acetone-water mixture. Thepurified ferric iron salt solution was then diluted in a ratio of 1:200(v/v) purified ferric iron solution to buffer solution. The buffer usedfor this dilution was prepared using equal volumes of 1.8 M potassiumbicarbonate and 0.9 M potassium carbonate. After dilution, 3.5 mL of thediluted ferric iron salt solution was placed in a clean cuvette, thenanalyzed in the spectrophotometer. The spectrum of the diluted ferriciron salt solution was taken from 190 nm to 1100 nm. The spectrum of thediluted ferric iron salt solution can be seen in FIG. 3. As shown in thefigure, there is a strong peak having a λ maximum of about 298 nm,centered at approximately 325 nm, extending from approximately 250 nm to500 nm. The strong peak decreases in absorbance from the peak at 298nanometers, tailing off into the visible part of the spectrum,eventually reaching approximately 0 absorbance at about 550 nm. Thisblue-violet absorbance in the near UV range explains the intense ambercolor of the suspected compound(s) in the purified aqueous alkalineferric iron salt solution.

Example 7

Pilot test of aqueous alkaline ferric iron solutions on biogascontaining high hydrogen sulfide levels.

A 70 liter volume of the alkaline aqueous ferric iron solution was usedto treat biogas containing ˜16,000 ppm hydrogen sulfide at a pulp andpaper mill. The same 70 liter solution had previously been used 4-5 daysper week for 7 months at a wastewater plant to scrub biogas containing150-450 ppm H₂S and had been regenerated repeatedly by oxidation withair. The pilot system was arranged as depicted in FIG. 2, with theexception that the sulfur filtration system was not included in thispilot.

Six scfm of warm, humid biogas entered the base of the scrubber columnvia a 2 inch PVC pipe and rose through a layer of plastic(polypropylene) packing, exiting the column via a 2 inch PVC pipe.Regenerated solution was pumped by an 8 liter per minute positivedisplacement pump to the top of the scrubber column, where a shower headtype sprayer distributed the alkaline ferric iron solution evenly on thetop of the packing. The solution trickled down through the packing, inclose contact with the rising stream of biogas. Hydrogen sulfide in thebiogas was absorbed into the solution and is believed to be quicklyconverted to ferrous sulfide (FeS) or ferric sulfide (Fe₂S₃). At thebottom of the column, the partially reduced solution accumulated into ashallow sump, where it was continuously pumped by an identical 8liter-per-minute positive displacement pump to the base of a 1 ftdiameter×30-inch tall regeneration column. Approximately 3 scfm of airwas pumped through a sparger into the regeneration column, regeneratingthe reduced alkaline iron solution to its active ferric form andsimultaneously oxidizing the captured sulfide to elemental sulfur. Theregenerated solution was then pumped to a primary accumulator and thento the top of the scrubber column, completing the H₂Scapture-regeneration cycle.

Due to the high H₂S levels present, colorimetric Draeger tubes were usedto measure H₂S in untreated gas. High range Draeger Glass Detector tubes(Model #CH28101) detect H₂S in the range 0.2 to 7% Vol. Measuring RangeMfr. The level measured in untreated biogas using the high range Draegertubes was ˜16-18,000 ppm H₂S in multiple samples. Hydrogen sulfidelevels in treated biogas were measured using an AMI digital H₂S monitorand also with low range Draeger tubes. Low range Draeger Glass Detectortubes (Model #810146) detect H₂S in the range 0.2 to 5 ppm. At 6 scfmgas flow, the AMI monitor consistently reported H₂S levels in treatedbiogas of ˜4 ppm and low range Draeger tubes recorded H₂S levels intreated biogas of 0-3 ppm in multiple samples.

Example 8

Carbon dioxide capture and release by aqueous alkaline ferric iron saltsolutions.

In both laboratory and field pilot studies, the aqueous alkaline ferriciron salt solutions used for H₂S scrubbing also capture carbon dioxideduring biogas gas H₂S-scrubbing cycles and release it during airregeneration cycles. CO₂ capture and release by the aqueous alkalineferric iron salt solution has been confirmed by pH studies in batchsamples in the laboratory, as well as by pH measurements and gasanalyses of regeneration air streams sampled during pilot studies. Arapid 0.75-1-unit pH drop occurs when aqueous alkaline ferric ironsolutions are exposed to biogas streams containing 20% or higher amountsof CO₂ during H₂S scrubbing experiments. It is believed that the pH dropin the scrubber solution occurs because CO₂, an acid gas, is capturedfrom the biogas, reacts with potassium carbonate to form potassiumbicarbonate in the scrubber solution, and thus decreases the pH of thesolution. During regeneration cycles, pH values of the scrubbingsolution rise by 0.75-1 pH units to stable levels as CO₂ is released tothe air. The graph provided in FIG. 4 shows regular pH swings over fourH₂S capture/air regeneration cycles in a batch-wise gas scrubbingexperiment conducted in our laboratory. Initial pH measurementspresented in this figure were later determined to be high by 1.5 pHunits. Corrected pH units are provided in FIG. 4.

CO₂ capture/release was confirmed by similar changes in pH levels duringscrubbing and regeneration cycles in pilot studies and by gaschromatographic (GC) analysis of gas samples from the air regenerationstream. The regeneration air stream was shown by GC to contain over 4%carbon dioxide, which had been removed from the biogas stream andreleased to the air during regeneration. Likewise, a 0.5 pH unit dropwas observed in the scrubber solution during the brief biogas scrubbingcycle, followed by a similar rise during air regeneration of the usedscrubber solution.

Example 9

Samples of the alkaline aqueous ferric iron salt concentrate werediluted 1:10 and 1:20 in buffer solutions containing various ratios of0.9M potassium carbonate and 1.8M potassium bicarbonate in distilledwater. The buffer ratios used were 100% (0.9144) carbonate, 100% (1.8M)bicarbonate and 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, and 1:4 vol:volcarbonate:bicarbonate.

All 1:20 concentrate:buffer solutions were initially fully soluble butafter 14 days iron oxide precipitates were observed in the 100% (1.8M)bicarbonate buffer, the 100% (0.9M) carbonate buffer and the 4:1 vol:volbicarbonate-carbonate buffer. After 34 days, iron precipitates were alsoobserved in the 3:1 vol:vol bicarbonate-carbonate buffer.

All 1:10 concentrate:buffer solutions remained soluble in all buffermixtures with the exception of the 1:10 dilution into 100% (0.9M)carbonate buffer, which remained soluble for 56 days, but thenprecipitated by day 70. From these results it appears that both the 1:10and 1:20 dilutions of iron salt concentrate into potassiumcarbonate-bicarbonate buffers are broadly and stably soluble across awide range of carbonate:bicarbonate ratios, but that the 1:20concentrate:buffer dilutions are less stable at very high and low-verylow ratios of carbonate-bicarbonate buffer.

TABLE 4 Results of Dilution of Concentrate with PotassiumCarbonate:Bicarbonate Buffer 100% (1.8M) 1 to 4 100% (0.9M) Bicarbonate(v:v) 1 to 3 1 to 2 1 to 1 2 to 1 3 to 1 4 to 1 Carbonate Iron saltconcentrate diluted 1:10 into potassium carbonate:bicarbonate buffer S(soluble) S S S S S S S PPT pH 9.23 pH 9.46 pH 9.57 pH 9.74 pH 10.03 pH10.34 pH 10.50 pH 10.67 pH 11.82 Iron salt concentrate diluted 1:20 intopotassium carbonate:bicarbonate buffer PPT PPT PPT S S S S S PPT(precipitate) pH 9.27 pH 9.48 pH 9.59 pH 9.78 pH 10.06 pH 10.35 pH 10.53pH 10.68 pH 11.86

While various embodiments of the invention described herein have beendescribed in detail, it is apparent that modifications and adaptationsof those embodiments will occur to those skilled in the art. However, itis to be expressly understood that such modifications and adaptationsare within the spirit and scope of the presently disclosed invention.

The invention claimed is:
 1. A method for removal of reduced sulfurcompounds from a fluid containing reduced sulfur compounds comprising:(a) contacting an alkaline aqueous ferric iron salt solution thatcontains anionic ferric iron-carbonate complexes with a reducedsulfur-containing fluid; (i) wherein the alkaline aqueous ferric ironsalt solution comprises ferric ions (Fe³⁺), potassium ions (K⁺),carbonate ions (CO₃ ²⁻) and bicarbonate ions (HCO^(3′)) and one or moreorganic additives; (ii) wherein a molar ratio of the potassium ions tothe ferric ions is at least 1.0; (iii) wherein a molar ratio of ferricions to a sum total of the one or more organic additives is greater than1; (iv) wherein the alkaline aqueous ferric iron salt solution is afully soluble aqueous alkaline ferric iron salt solution; (v) whereinthe alkaline aqueous ferric iron salt solution has a pH of at least 8:(b) producing, due to the contacting, a reduced alkaline iron solution,wherein the producing comprises: (i) forming one or more iron sulfidecompounds in the alkaline aqueous ferric iron salt solution to therebyremove at least a portion of the reduced sulfur compounds from thereduced sulfur-containing fluid; and (ii) oxidizing at least a portionof the at least one reduced sulfur compound and reducing at least aportion of the ferric ions to ferrous ions (Fe²⁺).
 2. The method ofclaim 1, further comprising, after removal of at least a portion of thereduced sulfur compounds from the fluid, (c) oxidizing at least aportion of ferrous iron formed in the at least partially reducedalkaline aqueous ferric iron solution to at least in part regenerate thealkaline aqueous ferric iron salt solution with concomitant oxidation ofat least a portion of the sulfide of iron sulfide in the at leastpartially reduced alkaline aqueous ferric iron solution to elementalsulfur.
 3. The method of claim 2, wherein the regenerated alkalineaqueous ferric iron salt solution is free of iron oxide-based or ironoxyhydroxide-based particles.
 4. The method of claim 2, whereinoxidizing at least a portion of the ferrous ions comprises exposing theat least partially reduced alkaline aqueous ferric iron solution to anoxidizing agent to oxidize at least a portion of the ferrous ionstherein to ferric ions, thereby producing a regenerated alkaline aqueousferric iron salt solution, wherein the exposing comprises producing theelemental sulfur.
 5. The method of claim 1, wherein the one or moreorganic additives are selected from the groups consisting of a polyol,an extract of a fruit, leaves or roots of a fruit, and any combinationthereof, a pectin from any source, and an aminopolycarboxylic acid. 6.The method of claim 1, wherein the alkaline aqueous ferric iron saltsolution has a pH of at least
 9. 7. The method of claim 1, wherein theat least one reduced sulfur compound comprises H₂S.
 8. The method ofclaim 1, wherein a flow of reduced sulfur-containing fluid is contactedwith the alkaline aqueous ferric iron salt solution for a selectedcontact time to remove the at least one reduced sulfur compound from thereduced sulfur-containing fluid to provide a purified fluid andthereafter iron sulfide(s) is oxidized in the at least partially reducedalkaline aqueous ferric iron solution to at least in part regenerate thealkaline aqueous ferric iron salt solution.
 9. The method of claim 1,wherein the alkaline aqueous ferric iron salt solution further comprisesnitrate ions (NO₃ ⁻).
 10. The method of claim 1, wherein a molarity offerric ions in the alkaline aqueous ferric iron salt solution is from0.005 to 3.0 mols/L.
 11. The method of claim 1, wherein the alkalineaqueous ferric iron salt solution comprises the one or more organicadditives, wherein a molar ratio of ferric ions to each organic additiveis 2 or more.